By confining water in nanopores, so narrow that the liquid cannot freeze, it is possible to explore its properties well below its homogeneous nucleation temperature T _H ≈ 235 K. In particular, the dynamical parameters of water can be measured down to 180 K, approaching the suggested glass transition temperature T _g ≈ 165 K. Here we present experimental evidence, obtained from Nuclear Magnetic Resonance and Quasi-Elastic Neutron Scattering spectroscopies, of a well defined decoupling of transport properties (the self-diffusion coefficient and the average translational relaxation time), which implies the breakdown of the Stokes–Einstein relation. We further show that such a non-monotonic decoupling reflects the characteristics of the recently observed dynamic crossover, at ≈225 K, between the two dynamical behaviors known as fragile and strong, which is a consequence of a change in the hydrogen bond structure of liquid water.

By confining water in a nanoporous structure so narrow that the liquid could not freeze, it is possible to study properties of this previously undescribed system well below its homogeneous nucleation temperature T _H = 231 K. Using this trick, we were able to study, by means of a Fourier transform infrared spectroscopy, vibrational spectra (HOH bending and OH-stretching modes) of deeply supercooled water in the temperature range 183 < T < 273 K. We observed, upon decreasing temperature, the building up of a new population of hydrogen-bonded oscillators centered around 3,120 cm ⁻¹ , the contribution of which progressively dominates the spectra as one enters into the deeply supercooled regime. We determined that the fractional weight of this spectral component reaches 50% just at the temperature, T _L ≈ 225 K, where the confined water shows a fragile-to-strong dynamic cross-over phenomenon [Ito, K., Moynihan, C. T., Angell, C. A. (1999) Nature 398:492–494]. Furthermore, the fact that the corresponding OH stretching spectral peak position of the low-density-amorphous solid water occurs exactly at 3,120 cm ⁻¹ [Sivakumar, T. C., Rice, S. A., Sceats, M. G. (1978) J. Chem. Phys. 69:3468–3476.] strongly suggests that these oscillators originate from existence of the low-density-liquid phase derived from the occurrence of the first-order liquid–liquid (LL) phase transition and the associated LL critical point in supercooled water proposed earlier by a computer molecular dynamics simulation [Poole, P. H., Sciortino, F., Essmann, U., Stanley, H. E. (1992) Nature 360:324–328].

It is becoming common practice to partition glass-forming liquids into two classes based on the dependence of the shear viscosity η on temperature T . In an Arrhenius plot, ln η vs 1/ T , a strong liquid shows linear behavior whereas a fragile liquid exhibits an upward curvature [super-Arrhenius (SA) behavior], a situation customarily described by using the Vogel–Fulcher–Tammann law. Here we analyze existing data of the transport coefficients of 84 glass-forming liquids. We show the data are consistent, on decreasing temperature, with the onset of a well-defined dynamical crossover η _× , where η _× has the same value, η _× ≈ 10 ³ Poise, for all 84 liquids. The crossover temperature, T _× , located well above the calorimetric glass transition temperature T _g , marks significant variations in the system thermodynamics, evidenced by the change of the SA-like T dependence above T _× to Arrhenius behavior below T _× . We also show that below T _× the familiar Stokes–Einstein relation D / T ∼ η ^-1 breaks down and is replaced by a fractional form D / T ∼ η ^{- ζ} , with ζ ≈ 0.85.

The temperature dependence of the density of water, ρ( T ), is obtained by means of optical scattering data, Raman and Fourier transform infrared, in a very wide temperature range, 30 < T < 373 K. This interval covers three regions: the thermodynamically stable liquid phase, the metastable supercooled phase, and the low-density amorphous solid phase, at very low T . From analyses of the profile of the OH stretching spectra, we determine the fractional weight of the two main spectral components characterized by two different local hydrogen bond structures. They are, as predicted by the liquid–liquid phase transition hypothesis of liquid water, the low- and the high-density liquid phases. We evaluate contributions to the density of these two phases and thus are able to calculate the absolute density of water as a function of T . We observe in ρ( T ) a complex thermal behavior characterized not only by the well known maximum in the stable liquid phase at T = 277 K, but also by a well defined minimum in the deeply supercooled region at 203 ± 5 K, in agreement with suggestions from molecular dynamics simulations.

Raman spectra in the O–H stretching band in normal and supercooled water have been investigated. Spectra are taken as a function of temperature in the range +95 to −24°C. Absolute Raman cross sections corrected for instrumental and physical factors are obtained. It is shown that the isotropic O–H stretching bands in the range +20 to +95 °C are due to the contribution of ’’open’’ (or tetrahedrically bonded) and ’’closed’’ water that are temperature independent. The percentage of open water α(T) is connected and interpreted in the frame of the Stanley site percolation model. As a consequence, the isobestic point is obtained. In the supercooled region, a third spectral contribution arises, which is centered near the main peak of the isotropic O–H band of ice. Such a contribution is tentatively explained as the presence in supercooled water of true ice, as a heterophase fluctuation.